Conductive polymer-containing liquid and method for producing the same, and conductive laminate and method for manufacturing the same

Abstract

To provide a conductive laminate having a conductive layer having improved conductivity and a manufacturing method capable of easily manufacturing the same, and a conductive polymer-containing liquid used in the manufacturing method and a method for manufacturing the same.SOLUTION: A conductive polymer-containing liquid contains a conductive composite body containing a π-conjugated conductive polymer and polyanion, water, a water-insoluble amine compound, a water-soluble amine compound, and one or more organic solvents, wherein the polyanion is modified by reaction with at least the water-insoluble amine compound out of the water-insoluble amine compound and the water-soluble amine compound. The organic solvent preferably contains alcohol. The organic solvent may further contain an ultraviolet curable acrylic resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a conductive polymer-containing liquid that contains a π-conjugated conductive polymer and a method for producing the same, and a conductive laminate and a method for producing the same. [Background technology]

[0002] A π-conjugated conductive polymer, whose main chain is composed of a π-conjugated system, forms a conductive complex by doping with a polyanion having an anion group, and becomes dispersible in water. A conductive film having a conductive layer can be manufactured by applying a conductive polymer-containing liquid (sometimes called a conductive polymer dispersion) containing the conductive complex to a film substrate or the like. In addition, an epoxy compound may be reacted with the conductive complex in order to increase the wettability of the conductive polymer-containing liquid to the film substrate or to increase the conductivity of the conductive layer to be formed. For example, Patent Document 1 discloses a method of improving the conductivity of a conductive complex by reacting a cyclic epoxy compound. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-111650 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a conductive laminate having a conductive layer with improved conductivity and a manufacturing method for easily manufacturing the same, as well as a conductive polymer-containing liquid used in the manufacturing method and a manufacturing method thereof. [Means for solving the problem]

[0005] [1] A conductive polymer-containing liquid comprising: a conductive complex including a π-conjugated conductive polymer and a polyanion; water; a water-insoluble amine compound; a water-soluble amine compound; and one or more organic solvents, wherein the polyanion is modified by a reaction with at least the water-insoluble amine compound out of the water-insoluble amine compound and the water-soluble amine compound. [2] The conductive polymer-containing liquid according to [1], wherein the organic solvent contains an alcohol. [3] The conductive polymer-containing liquid according to [1] or [2], further comprising an ultraviolet-curable acrylic resin. [4] The conductive polymer-containing liquid according to any one of [1] to [3], wherein the organic solvent contains an organic solvent having a boiling point of 100° C. or higher. [5] The conductive polymer-containing liquid according to any one of [1] to [4], wherein a mass ratio represented by (the water-insoluble amine compound / the water-soluble amine compound) is 2 or more and 20 or less. [6] The conductive polymer-containing liquid according to any one of [1] to [5], wherein the water-soluble amine compound includes an amine compound having two or more heteroatoms other than carbon atoms in the molecule. [7] The conductive polymer-containing liquid according to any one of [1] to [6], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene) or the polyanion is polystyrenesulfonic acid. [8] A method for producing a conductive polymer-containing liquid, comprising: adding an organic solvent, a water-insoluble amine compound, and a water-soluble amine compound to a conductive polymer dispersion liquid in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium; and reacting at least the water-insoluble amine compound with the polyanion. [9] A method for producing a conductive laminate, comprising applying the conductive polymer-containing liquid according to any one of [1] to [7] to at least a part of a surface of a substrate.

[10] A conductive laminate comprising a substrate and a conductive layer formed on at least a portion of the surface of the substrate, the conductive layer being a cured layer of the conductive polymer-containing liquid according to any one of [1] to [7]. Effect of the Invention

[0006] According to the conductive polymer-containing liquid of the present invention and the method for producing a conductive laminate using the same, a conductive laminate having a conductive layer with excellent conductivity can be easily produced. According to the method for producing a conductive polymer-containing liquid of the present invention, the above-mentioned conductive polymer-containing liquid can be easily produced.

[0007] This invention is believed to contribute to SDGs Goal 12, "Responsible Consumption and Production."

[0008] In this specification and claims, the lower limit and upper limit of a numerical range indicated with "to" are included in the numerical range. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] ≪Conductive polymer-containing liquid≫ A first aspect of the present invention is a conductive polymer-containing liquid that contains a conductive complex including a π-conjugated conductive polymer and a polyanion, water, a water-insoluble amine compound, a water-soluble amine compound, and one or more organic solvents, and the polyanion is modified by a reaction with at least the water-insoluble amine compound out of the water-insoluble amine compound and the water-soluble amine compound. In the conductive polymer-containing liquid of this embodiment, the conductive complex may be in a dispersed state or in a dissolved state, and no distinction is made between the two unless otherwise specified.

[0010] <π-conjugated conductive polymers> The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention and is an organic polymer whose main chain is composed of a π-conjugated system, and examples thereof include polypyrrole-based conductive polymers, polythiophene-based conductive polymers, polyacetylene-based conductive polymers, polyphenylene-based conductive polymers, polyphenylenevinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophenevinylene-based conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

[0011] Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly(3-chlorothiophene), and poly(3-iodothiophene). thiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), oxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-di dodecyloxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), and poly(3-methyl-4-carboxybutylthiophene). Examples of polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole), poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), and poly(3-methyl-4-hexyloxypyrrole). Examples of polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid). Among the above-mentioned π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferable from the viewpoints of conductivity, transparency, and heat resistance. The conductive composite may contain one type of π-conjugated conductive polymer, or two or more types of polymers.

[0012] <Polyanion> A polyanion is a polymer having two or more monomer units each having an anionic group in the molecule. The anionic group of the polyanion functions as a dopant for a π-conjugated conductive polymer, improving the conductivity of the π-conjugated conductive polymer. The anion group of the polyanion is preferably a sulfo group or a carboxy group. Specific examples of such polyanions include polymers having a sulfo group, such as polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (for example, poly(4-sulfobutyl methacrylate, polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), and polyisoprene sulfonic acid; and polymers having a carboxy group, such as polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprene carboxylic acid. These may be homopolymers or copolymers of two or more kinds. Among these polyanions, polymers having a sulfo group are preferred, and polystyrene sulfonic acid is more preferred, since they can provide higher electrical conductivity. The conductive complex may be composed of one type of polyanion or two or more types of polyanions. The mass average molecular weight of the polyanion is preferably from 20,000 to 1,000,000, more preferably from 100,000 to 500,000. The mass average molecular weight is the average molecular weight based on mass measured by gel permeation chromatography and calculated in terms of polystyrene.

[0013] A conductive complex is formed by doping a polyanion into a π-conjugated conductive polymer. However, in the polyanion, some anion groups are not doped into the π-conjugated conductive polymer, and the polyanion has excess anion groups that are not involved in the doping. Since these excess anion groups are hydrophilic groups, the conductive complex has high water dispersibility and low organic solvent dispersibility before reacting with an amine compound as described below. When the number of all anionic groups in the polyanion is taken as 100 mol %, the excess anionic groups are preferably from 30 mol % to 90 mol %, more preferably from 45 mol % to 75 mol %.

[0014] In the polyanion of the present invention, the excess anion groups of the polyanion that are not involved in the dope (hereinafter, also referred to as "part of the anion groups") are modified by reaction with at least a water-insoluble amine compound among a water-insoluble amine compound and a water-soluble amine compound. That is, the polyanion of the present invention has a substituent (B) formed by reaction between at least a water-insoluble amine compound and a part of the anion groups.

[0015] (Substituent B) Although it is not necessarily easy to perform a detailed analysis of the conductive composite, it is presumed that the substituent (B) is a group represented by the following formula (B).

[0016] -H.N. + R 11 R 12 R 13 (B) [In formula (B), R 11 ~R 13 are each independently a hydrogen atom or a hydrocarbon group which may have a substituent, provided that R 11 ~R 13 At least one of the groups is a hydrocarbon group which may have a substituent.]

[0017] In the substituent (B), the bond at the left end represents the bond between the negative charge of the anionic group and the positive charge of the amine compound. Examples of anionic groups that can be negatively charged include "-SO3 - " is an anionic group in which an active proton is bonded to an oxygen atom.

[0018] R in chemical formula (B) 11 ~R 13 is a hydrogen atom or a hydrocarbon group which may have a substituent. 11 ~R 13 is a substituent derived from an amine compound described later. Examples of the hydrocarbon group in chemical formula (B) include an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the substituent on the aliphatic hydrocarbon group include a phenyl group and a hydroxyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Examples of the substituent on the aromatic hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and a hydroxyl group.

[0019] In this specification and claims, a water-soluble amine compound is an amine compound that dissolves in 100 g of water at 20°C in an amount of 1 g or more, and a water-insoluble amine compound is an amine compound that dissolves in 100 g of water at 20°C in an amount of less than 1 g. The conductive polymer-containing liquid of this embodiment may contain one type of water-soluble amine compound or two or more types of water-insoluble amine compounds. The conductive polymer-containing liquid of this embodiment may contain one type of water-insoluble amine compounds or two or more types of water-insoluble amine compounds. Hereinafter, water-soluble amine compounds and water-insoluble amine compounds may be collectively referred to simply as "amine compounds."

[0020] The amine compound is preferably at least one selected from the group consisting of primary amines, secondary amines, and tertiary amines. Examples of primary amines include aniline, toluidine, benzylamine, and ethanolamine. Examples of secondary amines include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, and dinaphthylamine. Examples of tertiary amines include triethanolamine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, triphenylamine, tribenzylamine, and trinaphthylamine. Among the amine compounds, tertiary amines are preferred because they can increase the electrical conductivity of the conductive composite of this embodiment, and at least one of trioctylamine and tributylamine is more preferred.

[0021] In order to improve dispersibility in organic solvents, particularly in low-polarity hydrocarbon solvents and ester solvents, the water-insoluble amine compound preferably has a substituent on the nitrogen atom having 4 or more carbon atoms, more preferably has a substituent on the nitrogen atom having 6 or more carbon atoms, and even more preferably has a substituent on the nitrogen atom having 8 or more carbon atoms. The upper limit of the carbon number of the substituent on the nitrogen atom is not particularly limited, and taking into consideration solubility in solvents and reactivity, it is, for example, preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less. In addition, the R 11 ~R 13 The total number of carbon atoms is preferably 6 to 33, more preferably 9 to 30, and further preferably 12 to 27. The number of carbon atoms in each of the substituents on the nitrogen atom may be the same or different.

[0022] The water-insoluble amine compound of this embodiment is preferably at least one selected from the group consisting of tributylamine, trioctylamine, tridodecylamine, didodecylamine, trihexylamine, and tridecylamine, for example. The above-mentioned suitable water-insoluble amine compounds further increase the conductivity of the conductive layer made of the conductive polymer-containing liquid of this embodiment.

[0023] From the viewpoint of exhibiting water solubility, the water-soluble amine compound of this embodiment preferably has 3 or less carbon atoms in the molecule. In addition, the number of heteroatoms (atoms other than carbon atoms, such as nitrogen atoms, oxygen atoms, sulfur atoms, etc.) in the molecule of the water-soluble amine compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Since the heteroatoms in the molecule have unpaired electron pairs, the solubility in water is increased by the formation of hydrogen bonds. Therefore, a water-soluble amine compound having 2 or more heteroatoms can exhibit water solubility even if the number of carbon atoms in the molecule is 4 or more. The upper limit of the number of the heteroatoms is not particularly limited, and for example, 10 or less can be mentioned as a guideline.

[0024] The water-soluble amine compound of this embodiment is preferably, for example, one or more selected from the group consisting of imidazole, vinylimidazole, triethanolamine, tris[2-(2-methoxyethoxy)ethyl]amine, ethanolamine, and ammonia. The above-mentioned suitable water-soluble amine compound further enhances the conductivity of the conductive layer made of the conductive polymer-containing liquid of this embodiment.

[0025] The combination of the water-insoluble amine compound and the water-soluble amine compound in this embodiment is not particularly limited, and examples thereof include a combination of one type each arbitrarily selected from the above-mentioned suitable amine compounds.

[0026] The content of the water-insoluble amine compound in the conductive polymer-containing liquid of this embodiment is preferably 10 parts by mass or more and 1,000 parts by mass or less, more preferably 30 parts by mass or more and 500 parts by mass or less, and even more preferably 50 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the total mass of the π-conjugated conductive polymer and the polyanion. When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite is sufficiently high, and the dispersibility in organic solvents is improved. When the content is equal to or less than the upper limit of the above range, a decrease in electrical conductivity due to unreacted amine compound can be prevented. Here, it is not necessary for all of the water-insoluble amine compounds to form the substituent (B), but it is preferable that at least a part of the compounds form the substituent (B) from the viewpoint of improving the dispersibility of the conductive composite in the organic solvent.

[0027] The content of the water-soluble amine compound in the conductive polymer-containing liquid of this embodiment is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total mass of the π-conjugated conductive polymer and the polyanion. When the content is within the above range, the conductivity of the conductive layer made of the conductive polymer-containing liquid of this embodiment is further increased. Here, the water-soluble amine compound may or may not form a substituent (B).

[0028] The ratio (X:Y) of the mass X of the water-insoluble amine compound to the mass Y of the water-soluble amine compound contained in the conductive polymer-containing liquid of this embodiment is preferably 10:0.1 to 10:5, more preferably 10:0.5 to 10:4, and even more preferably 10:1 to 10:3. When the content is within the above range, the conductivity of the conductive layer made of the conductive polymer-containing liquid of this embodiment is further increased.

[0029] In the conductive polymer-containing liquid of this embodiment, the content of the polyanion is preferably in the range of 1 part by mass to 1000 parts by mass, more preferably 10 parts by mass to 700 parts by mass, and even more preferably 100 parts by mass to 500 parts by mass, relative to 100 parts by mass of the π-conjugated conductive polymer. If the content of the polyanion is equal to or greater than the lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, and the conductivity becomes higher. On the other hand, if the content of the polyanion is equal to or less than the upper limit, the amount of anion groups not involved in doping is appropriately suppressed, and it becomes easy to react the anion groups with an amine compound to convert the conductive complex to hydrophobicity.

[0030] The content of the conductive complex relative to the total mass of the conductive polymer-containing liquid is, for example, preferably 0.01 mass % or more and 2 mass % or less, more preferably 0.05 mass % or more and 1.5 mass % or less, and even more preferably 0.1 mass % or more and 1 mass % or less.

[0031] <Dispersion medium> The dispersion medium contained in the conductive polymer-containing liquid of this embodiment is a liquid agent that disperses or dissolves the conductive composite described above. In this specification, the term "dispersion" may be used without distinguishing between dispersion and dissolution, and the term "dispersion medium" may be used without distinguishing between the dispersion medium and the solvent. Therefore, the dispersion medium may be referred to as a solvent.

[0032] The dispersion medium includes water and one or more organic solvents. The conductive complex contained in the conductive polymer-containing liquid is hydrophobized as described above, and therefore has excellent dispersibility in organic solvents.

[0033] (Organic solvent) The organic solvent in this embodiment may be a water-soluble organic solvent, a water-insoluble organic solvent, or a mixed solvent of a water-soluble organic solvent and a water-insoluble organic solvent. Here, the water-soluble organic solvent is an organic solvent that dissolves in an amount of 1 g or more in 100 g of water at 20° C., and the water-insoluble organic solvent is an organic solvent that dissolves in an amount of less than 1 g in 100 g of water at 20° C. The organic solvent in this embodiment is preferably a water-soluble organic solvent since the solubility of the amine compound is increased.

[0034] Examples of the water-soluble organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, nitrogen atom-containing solvents, and ester-based solvents. Examples of alcohol-based solvents (alcohols) include methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Examples of the ether solvent include diethyl ether, dimethyl ether, propylene glycol dialkyl ether, and diethylene glycol diethyl ether. Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, and diacetone alcohol. Examples of the nitrogen atom-containing solvent include N-methylpyrrolidone, dimethylacetamide, and dimethylformamide. The water-soluble organic solvent may be used alone or in combination of two or more kinds. The water-soluble organic solvent is preferably an alcohol-based solvent, a ketone-based solvent, or an ester-based solvent, since this improves the coatability of the conductive polymer-containing liquid on the substrate.

[0035] Examples of the non-water-soluble organic solvent include hydrocarbon solvents, etc. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include hexane, cyclohexane, pentane, heptane, octane, nonane, decane, and dodecane. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, and isopropylbenzene. The water-insoluble organic solvents may be used alone or in combination of two or more kinds.

[0036] The content of the organic solvent relative to the total mass of the dispersion medium of the conductive polymer-containing liquid of this embodiment is preferably more than 50 mass%, more preferably 70 mass% to 100 mass%, and even more preferably 80 mass% to 99.9 mass%. When the content ratio of the organic solvent is within the above range, the hydrophobized conductive composite can be easily dispersed, and the conductive layer can be easily formed.

[0037] (High boiling point solvent) The conductive polymer-containing liquid of this embodiment may contain a high-boiling point solvent having a boiling point of 100° C. or more at 1 atmosphere (101,325 Pascals). The boiling point of the high-boiling point solvent is preferably 250° C. or less. By containing a high-boiling point solvent, effects such as improved conductivity can be obtained. The conductive polymer-containing solution of this embodiment preferably contains a high boiling point solvent and an organic solvent other than the high boiling point solvent (an organic solvent having a boiling point of less than 100° C. at 1 atmospheric pressure). The conductive polymer-containing liquid of this embodiment may contain one type of high boiling point solvent, or two or more types of high boiling point solvents. The conductive polymer-containing liquid of this embodiment may contain one type of organic solvent other than the high-boiling point solvent, or may contain two or more types of organic solvent.

[0038] Examples of high boiling point solvents include water-soluble organic solvents and water-insoluble organic solvents, the definitions of which are the same as those described above.

[0039] Examples of the high-boiling water-soluble organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, nitrogen atom-containing solvents, and sulfur atom-containing solvents. Examples of alcohol-based solvents include polyhydric alcohols such as ethylene glycol (boiling point 198°C), 1,2-propanediol (also known as propylene glycol, boiling point 188°C), 1,3-propanediol (boiling point 214°C), 1,2-butanediol (boiling point 194°C), 1,3-butanediol (boiling point 207°C), 1,4-butanediol (boiling point 228°C), dipropylene glycol (boiling point 232°C, mixture of isomers), and diethylene glycol (boiling point 245°C). Examples of ether solvents include propylene glycol monoethyl ether (boiling point: 132.8° C.), diethylene glycol dimethyl ether (boiling point: 162° C.), and diethylene glycol diethyl ether (boiling point: 188° C.). Examples of ketone solvents include methyl amyl ketone (boiling point 151° C.) and diacetone alcohol (boiling point 168° C.). Examples of nitrogen atom-containing solvents include N-methylpyrrolidone (boiling point 202° C.), N-methylacetamide (boiling point 206° C.), dimethylacetamide (boiling point 165° C.), and N,N-dimethylformamide (boiling point 153° C.). An example of the sulfur atom-containing solvent is dimethyl sulfoxide (boiling point: 189° C.).

[0040] Examples of the high-boiling point water-insoluble organic solvent include hydrocarbon solvents, etc. Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent include nonane (boiling point 151° C.), decane (boiling point 174° C.), and dodecane (boiling point 216° C.). Examples of aromatic hydrocarbon solvents include propylbenzene (boiling point 159° C.) and isopropylbenzene (boiling point 152° C.).

[0041] Among the above examples, alcohol-based or ether-based high-boiling point solvents are preferred because they provide a greater effect of improving electrical conductivity.

[0042] The content ratio of the high-boiling point solvent relative to a total of 10 parts by mass of the amine compounds contained in the conductive polymer-containing liquid of this embodiment is preferably 100 parts by mass to 10,000 parts by mass, more preferably 500 parts by mass to 5,000 parts by mass, and even more preferably 800 parts by mass to 3,000 parts by mass. When in the above range, the conductivity of the formed conductive layer is further improved.

[0043] The content of the high-boiling point solvent relative to the total mass of the conductive polymer-containing liquid of this embodiment is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, and even more preferably 10% by mass to 20% by mass. When in the above range, the conductivity of the formed conductive layer is further improved.

[0044] The ratio of the high boiling point solvent and the organic solvent other than the high boiling point solvent contained in the conductive polymer-containing liquid of this embodiment is preferably such that the mass of the high boiling point solvent (M1) is less than the mass of the organic solvent other than the high boiling point solvent (M2). The M2 / M1 ratio is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5. When the content is within the above range, the conductivity of the conductive layer formed can be further increased.

[0045] When the conductive polymer-containing liquid of this embodiment contains an ultraviolet curable resin described below, it preferably contains a high boiling point solvent.

[0046] <UV-curable acrylic resin> The conductive polymer-containing liquid of this embodiment may contain an ultraviolet-curable acrylic resin. The ultraviolet-curable acrylic resin is a monomer or oligomer (a low polymer having a weight-average molecular weight of 10,000 or less) that is cured by ultraviolet irradiation during the formation of the conductive layer to become an acrylic resin. The conductive polymer-containing liquid of this embodiment may contain only one type of ultraviolet-curable acrylic resin, or two or more types of ultraviolet-curable acrylic resin.

[0047] The ultraviolet-curable acrylic resin is preferably a polyfunctional (meth)acrylate monomer. In this specification, "(meth)acrylate" means "acrylate and / or methacrylate", "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid", "(meth)acrylic resin" means "acrylic resin and / or methacrylic resin", "(meth)acryloyl group" means "acryloyl group and / or methacryloyl group", and "(meth)acryloyloxy group" means "acryloyloxy group and / or methacryloyloxy group".

[0048] The polyfunctional (meth)acrylate monomer is not particularly limited as long as it is a monomer having two or more (meth)acryloyl groups, and examples thereof include bifunctional (meth)acrylates (a1), trifunctional (meth)acrylates (a2), tetrafunctional to hexafunctional (meth)acrylates (a3), and heptafunctional to decafunctional (meth)acrylates (a4).

[0049] Examples of the bifunctional (meth)acrylate (a1) include esters of polyhydric alcohols and (meth)acrylic acid [e.g., di(meth)acrylate of glycol, di(meth)acrylate of glycerin, di(meth)acrylate of trimethylolpropane, di(meth)acrylate of 3-hydroxy-1,5-pentanediol, and di(meth)acrylate of 2-hydroxy-2-ethyl-1,3-propanediol]; esters of alkylene oxide adducts of polyhydric alcohols and (meth)acrylic acid [e.g., di(meth)acrylate of ethylene oxide adduct of trimethylolpropane, and di(meth)acrylate of ethylene oxide adduct of glycerin]; hydroxyl group-containing epoxy acrylates at both ends; esters of polyhydric alcohols, (meth)acrylic acid, and hydroxycarboxylic acids [e.g., hydroxypivalic acid neopentyl glycol di(meth)acrylate]. Here, it is not necessary to react all of the hydroxyl groups of the polyhydric alcohol with (meth)acrylic acid or an alkylene oxide adduct, and some hydroxyl groups may remain unreacted.

[0050] Examples of the trifunctional (meth)acrylate (a2) include tri(meth)acrylate of glycerin, tri(meth)acrylate of trimethylolpropane, tri(meth)acrylate of pentaerythritol, and tri(meth)acrylate of an ethylene oxide adduct of trimethylolpropane.

[0051] Examples of the tetra- to hexafunctional (meth)acrylate (a3) ​​include tetra(meth)acrylate of pentaerythritol, penta(meth)acrylate of dipentaerythritol, hexa(meth)acrylate of dipentaerythritol, tetra(meth)acrylate of an ethylene oxide adduct of dipentaerythritol, penta(meth)acrylate of an ethylene oxide adduct of dipentaerythritol, and penta(meth)acrylate of a propylene oxide adduct of dipentaerythritol.

[0052] Examples of the hepta-to-decafunctional (meth)acrylate compound (a4) include a reaction product of a diisocyanate compound, such as a compound obtained by reacting dipentaerythritol penta(meth)acrylate with hexamethylene diisocyanate, with a hydroxyl group-containing polyfunctional (meth)acrylate compound.

[0053] The content of the ultraviolet-curable acrylic resin relative to the total mass of the conductive polymer-containing liquid in this embodiment is preferably 5% by mass to 40% by mass, more preferably 10% by mass to 30% by mass, and even more preferably 15% by mass to 25% by mass. When the content is at least as large as the lower limit of the above range, the film strength of the conductive layer to be formed can be further increased. When the content is equal to or less than the upper limit of the above range, the content of the conductive complex in the conductive layer to be formed can be increased, so that the conductivity of the conductive layer can be further increased.

[0054] It is preferable to contain a photopolymerization initiator that generates radicals by irradiation with ultraviolet light in combination with the ultraviolet-curable acrylic resin.

[0055] (Other additives) The conductive polymer-containing liquid of this embodiment may contain other known additives. The additives are not particularly limited as long as the effects of the present invention can be obtained. For example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, etc. can be used. The surfactant may be a nonionic, anionic or cationic surfactant, with the nonionic surfactant being preferred from the standpoint of storage stability. A polymer surfactant such as polyvinylpyrrolidone may also be added. Examples of the inorganic conductive agent include metal ions, conductive carbon, etc. Metal ions can be generated by dissolving a metal salt in water. The antifoaming agent includes silicone resin, polydimethylsiloxane, silicone oil, and the like. The coupling agent may be a silane coupling agent having a vinyl group or an amino group. When the conductive polymer-containing liquid of this embodiment contains the additive, the content ratio thereof is appropriately determined depending on the type of additive, and can be, for example, in the range of 0.001 parts by mass or more and 5 parts by mass or less relative to 100 parts by mass in total of the π-conjugated conductive polymer and the polyanion.

[0056] <Method for producing conductive polymer-containing liquid> A second aspect of the present invention is a method for producing a conductive polymer-containing liquid, the method comprising adding an organic solvent, a water-insoluble amine compound, and a water-soluble amine compound to a conductive polymer dispersion liquid in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium, and reacting at least the water-insoluble amine compound with the polyanion. According to the production method of this embodiment, the conductive polymer-containing liquid of the first embodiment can be produced.

[0057] When the water-insoluble amine compound and the water-soluble amine compound are added to the conductive polymer dispersion, at least the water-insoluble amine compound reacts with some of the anion groups of the polyanion. This forms a substituent (B) and makes the conductive complex hydrophobic. For this reason, by adding an organic solvent during the reaction, a conductive polymer-containing liquid can be obtained in which the conductive complex after the reaction is stably dispersed or dissolved in the dispersion medium. Here, the organic solvent added during the reaction is preferably the "organic solvent other than the high boiling point solvent."

[0058] The amount of the water-insoluble amine compound added is preferably 10 parts by mass or more and 1,000 parts by mass or less, more preferably 30 parts by mass or more and 500 parts by mass or less, and even more preferably 50 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the total mass of the π-conjugated conductive polymer and the polyanion. When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite is sufficiently high, and the dispersibility in organic solvents is improved. When the content is equal to or less than the upper limit of the above range, a decrease in electrical conductivity due to unreacted amine compound can be prevented.

[0059] The amount of the water-soluble amine compound added is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total mass of the π-conjugated conductive polymer and the polyanion. When the content is within the above range, the conductivity of the conductive layer made of the conductive polymer-containing liquid of this embodiment is further increased.

[0060] The mass ratio (X:Y) of the amount X of the water-insoluble amine compound to the amount Y of the water-soluble amine compound is preferably 10:0.1 to 10:5, more preferably 10:0.5 to 10:4, and further preferably 10:1 to 10:3. When the content is within the above range, the conductivity of the conductive layer made of the conductive polymer-containing liquid of this embodiment is further increased.

[0061] The total amount of the water-insoluble amine compound and the water-soluble amine compound to be added is preferably 10 parts by mass or more and 1,000 parts by mass or less, more preferably 40 parts by mass or more and 500 parts by mass or less, and even more preferably 80 parts by mass or more and 300 parts by mass or less, relative to 100 parts by mass of the π-conjugated conductive polymer and the polyanion. When it is at least the lower limit of the above range, the hydrophobicity of the conductive composite is sufficiently high, and the dispersibility in organic solvents is improved. When the content is equal to or less than the upper limit of the above range, a decrease in electrical conductivity due to unreacted amine compound can be prevented.

[0062] The conductive polymer dispersion used as the "raw material" in this embodiment is a dispersion in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium. Here, the aqueous dispersion medium of the conductive polymer dispersion is water or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol-based solvents, ketone-based solvents, and ester-based solvents. The aqueous dispersion medium may contain one type of water-soluble organic solvent or two or more types of water-soluble organic solvents. The content of water relative to the total mass of the aqueous dispersion medium of the conductive polymer dispersion is preferably more than 50 mass%, more preferably 60 mass% or more, and even more preferably 80 mass% or more, and may be 100 mass%.

[0063] The conductive polymer dispersion can be obtained, for example, by chemically oxidizing and polymerizing a monomer that forms a π-conjugated conductive polymer in an aqueous solution of a polyanion. Alternatively, a commercially available conductive polymer dispersion can be used. The chemical oxidation polymerization can use a known catalyst and oxidizing agent. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

[0064] A high boiling point organic solvent and an ultraviolet curable acrylic resin may be further added to the conductive polymer-containing liquid obtained by the above reaction.

[0065] <Conductive laminate> A third aspect of the present invention is a conductive laminate comprising a substrate and a conductive layer formed on at least a portion of the surface of the substrate, the conductive layer being a cured layer of the conductive polymer-containing liquid of the first aspect.

[0066] [Conductive layer] The conductive layer may be formed over the entire surface of any surface of the substrate, or over a portion of the entire surface. In the conductive film, it is preferable that a conductive layer of substantially uniform thickness is formed over substantially the entire surface of one surface or the other surface of the film substrate. When a conductive layer is formed only over a portion of the surface of the substrate, the conductive layer may be, for example, a fine conductive pattern such as a circuit or an electrode, or the conductive layer may be provided on the same surface and the conductive layer may be not provided on the same surface and may be roughly divided.

[0067] The average thickness of the conductive layer is, for example, preferably 10 nm or more and 100 μm or less, more preferably 20 nm or more and 50 μm or less, and even more preferably 30 nm or more and 30 μm or less. When the average thickness of the conductive layer is equal to or greater than the lower limit, high conductivity can be exhibited, and when the average thickness is equal to or less than the upper limit, the adhesion of the conductive layer to the substrate is further improved.

[0068] [Base material] The substrate may be a substrate made of an insulating material or a substrate made of a conductive material. The shape of the substrate is not particularly limited, and examples thereof include a shape mainly having a flat surface, such as a film or a substrate. Examples of insulating materials include glass, synthetic resin, and ceramics. The conductive material may be a metal, a conductive metal oxide, carbon, or the like.

[0069] (Film substrate) When a film substrate is used as the substrate, the conductive laminate becomes a conductive film. The film substrate may be, for example, a plastic film made of a synthetic resin, such as ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene-based elastomer, polyester-based elastomer, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propionate, etc. From the viewpoint of improving the adhesion between the film substrate and the conductive layer, the synthetic resin for the film substrate is preferably a polyester resin, and among these, polyethylene terephthalate is preferable.

[0070] The synthetic resin for the film substrate may be either amorphous or crystalline. The film substrate may be either unstretched or stretched. The film substrate may be subjected to a surface treatment such as a corona discharge treatment, a plasma treatment, or a flame treatment in order to further improve the adhesion of the conductive layer.

[0071] The average thickness of the film substrate is preferably 5 μm to 500 μm, more preferably 20 μm to 200 μm. If the average thickness of the film substrate is equal to or more than the lower limit, the film is less likely to break, and if the average thickness is equal to or less than the upper limit, the film can have sufficient flexibility. The average thickness of the film substrate is calculated by measuring the thickness at 10 randomly selected points and averaging the measured values.

[0072] (Glass substrate) Examples of the glass substrate include an alkali-free glass substrate, a soda-lime glass substrate, a borosilicate glass substrate, and a quartz glass substrate. If the substrate contains an alkali component, the conductivity of the conductive layer tends to decrease, so among the above glass substrates, an alkali-free glass is preferred. Here, the alkali-free glass refers to a glass composition in which the content of the alkali component is 0.1 mass% or less with respect to the total mass of the glass composition.

[0073] The average thickness of the glass substrate is preferably from 100 μm to 3000 μm, more preferably from 100 μm to 1000 μm. If the average thickness of the glass substrate is equal to or more than the lower limit, the substrate is less likely to break, and if the average thickness is equal to or less than the upper limit, the substrate can contribute to a thinner conductive laminate. The average thickness of the glass substrate is calculated by measuring the thickness at 10 randomly selected points and averaging the measured values.

[0074] <Method for manufacturing conductive laminate> A fourth aspect of the present invention is a method for producing a conductive laminate, the method including applying the conductive polymer-containing liquid of the first aspect to at least a part of a surface of a substrate to form a conductive layer. The conductive laminate of the third aspect can be produced by the production method of this aspect.

[0075] Examples of a method for applying (coating) the conductive polymer-containing liquid on an arbitrary surface of a substrate include a method using a coater such as a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, an air doctor coater, a knife coater, a blade coater, a cast coater, or a screen coater; a method using a sprayer such as an air spray, an airless spray, or a rotor dampening; and an immersion method such as dipping.

[0076] The amount of conductive polymer-containing liquid applied to the substrate is not particularly limited, but taking into consideration uniform and even application, conductivity, and film strength, a solid content of 0.01 g / m 2 More than 10.0g / m 2 The following ranges are preferred:

[0077] The conductive layer can be formed by drying the coating film made of the conductive polymer-containing liquid applied onto the substrate to remove at least a portion of the dispersion medium and curing the coating film. Methods for drying the coating film include heat drying, vacuum drying, etc. Examples of heat drying that can be used include hot air heating and infrared heating. When applying heat drying, the heating temperature is appropriately set depending on the dispersion medium used, but is usually within the range of 50° C. to 200° C. Here, the heating temperature is the set temperature of the drying device. A suitable drying time within the above heating temperature range is preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 15 minutes. After drying, the UV-curable resin contained in the coating film may be cured by UV irradiation. EXAMPLES

[0078] (Production Example 1) Production of polystyrene sulfonic acid 206 g of sodium styrenesulfonate was dissolved in 1000 ml of ion-exchanged water, and while stirring at 80° C., 1.14 g of an oxidizing agent solution of ammonium persulfate previously dissolved in 10 ml of water was added dropwise over 20 minutes, and the solution was stirred for 12 hours. 1000ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate solution, and about 1000ml of the solvent from the obtained polystyrene sulfonic acid solution was removed by ultrafiltration. Next, 2000ml of ion-exchanged water was added to the remaining liquid, and about 2000ml of the solvent was removed by ultrafiltration to wash the polystyrene sulfonic acid with water. This washing operation was repeated three times. Water in the resulting solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

[0079] (Production Example 2) A solution of 0.5 g of 3,4-ethylenedioxythiophene and 1.5 g of polystyrene sulfonic acid dissolved in 15.0 g of ion-exchanged water was mixed at 20° C. Next, 89.5 g of ion-exchanged water was added. The resulting mixed solution was kept at 20°C and, while stirring, a solution of 0.03 g of ferric sulfate dissolved in 4.97 g of ion-exchanged water and a solution of 1.1 g of ammonium persulfate dissolved in 8.9 g of ion-exchanged water were slowly added, and the resulting reaction solution was stirred for 24 hours to react. By the above reaction, a conductive polymer dispersion liquid containing a conductive complex (PEDOT-PSS) containing poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, which are π-conjugated conductive polymers, and water, which is a dispersion medium, was obtained. To this conductive polymer dispersion, 13.2 g of Duolite C255LFH (a cation exchange resin manufactured by Sumika Chemtex Corporation) and 13.2 g of Duolite A368S (anion exchange resin manufactured by Sumika Chemtex Corporation) were added, and the ion exchange resin was removed by filtration to obtain a conductive polymer dispersion from which the oxidant and catalyst had been removed (conductive complex concentration: approximately 1.3% by mass).

[0080] Example 1 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.824 g of isopropanol, 0.16 g of trioctylamine, and 0.016 g of imidazole were mixed to obtain a conductive polymer-containing liquid containing a product formed by reaction of each amine compound with PEDOT-PSS. Next, the solution was applied to a PET film (Lumirror T-60, manufactured by Toray Industries, Inc.) using a bar coater #4, and dried at 120° C. for 1 minute to obtain a conductive film. The surface resistance of this conductive film was measured, and the results are shown in Table 1. Next, 64.2 g of the conductive polymer-containing liquid, 20 g of dipentaerythritol hexaacrylate, 0.8 g of Irgacure 184 (BASF, photopolymerization initiator), and 15 g of propylene glycol monoethyl ether (boiling point: 132.8°C) were mixed to obtain a coating material. Next, the coating material was applied to a PET film using a #8 bar coater, dried at 100°C for 1 minute, and irradiated with 400 mJ of ultraviolet light to obtain a conductive film (conductive hard coat film). The results of measuring the surface resistance are shown in Table 1.

[0081] Example 2 15g of the conductive polymer dispersion obtained in Production Example 2, 84.808g of isopropanol, 0.16g of trioctylamine, and 0.032g of imidazole were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0082] Example 3 15g of the conductive polymer dispersion obtained in Production Example 2, 84.792g of isopropanol, 0.16g of trioctylamine, and 0.048g of imidazole were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0083] Example 4 15g of the conductive polymer dispersion obtained in Production Example 2, 84.824g of isopropanol, 0.16g of trioctylamine, and 0.016g of vinylimidazole were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0084] Example 5 15g of the conductive polymer dispersion obtained in Production Example 2, 84.824g of isopropanol, 0.16g of trioctylamine, and 0.016g of triethanolamine were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each was measured. The results are shown in Table 1.

[0085] Example 6 15g of the conductive polymer dispersion obtained in Production Example 2, 84.824g of isopropanol, 0.16g of trioctylamine, and 0.016g of tris[2-(2-methoxyethoxy)ethyl]amine were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0086] Example 7 15g of the conductive polymer dispersion obtained in Production Example 2, 84.736g of isopropanol, 0.24g of tridodecylamine, and 0.024g of imidazole were mixed to obtain a conductive polymer-containing solution containing the product of the reaction of each amine compound with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0087] Example 8 15g of the conductive polymer dispersion obtained in Production Example 2, 84.824g of isopropanol, 0.16g of didodecylamine, and 0.016g of imidazole were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0088] Example 9 30 g of the conductive polymer dispersion obtained in Production Example 2, 69.648 g of isopropanol, 0.32 g of trioctylamine, and 0.032 g of imidazole were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0089] Example 10 15g of the conductive polymer dispersion obtained in Production Example 2, 15g of methanol, 69.824g of methyl ethyl ketone, 0.16g of trioctylamine, and 0.016g of imidazole were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0090] Comparative Example 1 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.84 g of isopropanol, and 0.16 g of trioctylamine were mixed to obtain a conductive polymer-containing solution containing a product of one type of amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0091] Comparative Example 2 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.76 g of isopropanol, and 0.24 g of tridodecylamine were mixed to obtain a conductive polymer-containing solution containing a product of one type of amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0092] Comparative Example 3 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.84 g of isopropanol, and 0.16 g of didodecylamine were mixed to obtain a conductive polymer-containing solution containing a product of one type of amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0093] Comparative Example 4 15g of the conductive polymer dispersion obtained in Production Example 2, 84.824g of isopropanol, 0.16g of trioctylamine, and 0.016g of tridodecylamine were mixed to obtain a conductive polymer-containing solution containing the product of each amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0094] Comparative Example 5 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.97 g of isopropanol, and 0.03 g of imidazole were mixed to prepare a conductive polymer-containing liquid. However, the conductive polymer settled and did not reach a dispersed state suitable for application, so the process was discontinued.

[0095] Comparative Example 6 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.957 g of isopropanol, and 0.043 g of vinylimidazole were mixed to prepare a conductive polymer-containing liquid. However, the conductive polymer settled and did not reach a dispersed state suitable for application, so the process was discontinued.

[0096] Comparative Example 7 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.932 g of isopropanol, and 0.068 g of triethanolamine were mixed to prepare a conductive polymer-containing liquid. However, the conductive polymer settled and did not reach a dispersed state suitable for application, so the process was discontinued.

[0097] Comparative Example 8 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.854 g of isopropanol, and 0.146 g of tris[2-(2-methoxyethoxy)ethyl]amine were mixed to prepare a conductive polymer-containing liquid. However, the conductive polymer settled and did not reach a dispersed state suitable for application, so the process was discontinued.

[0098] Comparative Example 9 15 g of the conductive polymer dispersion obtained in Production Example 2, 84.967 g of isopropanol, 0.03 g of imidazole, and 0.003 g of vinylimidazole were mixed to prepare a conductive polymer-containing liquid. However, the conductive polymer settled and did not reach a dispersed state suitable for application, so the process was discontinued.

[0099] Comparative Example 10 30 g of the conductive polymer dispersion obtained in Production Example 2, 69.68 g of isopropanol, and 0.32 g of trioctylamine were mixed to obtain a conductive polymer-containing solution containing a product of one type of amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0100] Comparative Example 11 15g of the conductive polymer dispersion obtained in Production Example 2, 15g of methanol, 69.84g of methyl ethyl ketone, and 0.16g of trioctylamine were mixed to obtain a conductive polymer-containing solution containing a product of one type of amine compound reacting with PEDOT-PSS. Using this, two types of conductive films were obtained in the same manner as in Example 1, and the surface resistance of each film was measured. The results are shown in Table 1.

[0101] [Measurement of surface resistance] For the conductive films prepared in each example, the surface resistance value of the conductive layer was measured using a resistivity meter (Hiresta manufactured by Nitto Seiko Analytech Co., Ltd.) under the condition of an applied voltage of 10 V. In the table, "2.0E+05" means "2.0×10 5 " and similarly for others. The units of measurement in the table are Ω / □.

[0102] [Table 1]

[0103] <Result> The conductive films of the examples, which were produced using a conductive polymer-containing liquid containing a conductive complex hydrophobized to be dispersible in an organic solvent by the addition of a water-insoluble amine compound and a water-soluble amine compound, had superior conductivity to the comparative examples. Comparative Examples 1 to 4, 10, and 11 contained a conductive complex hydrophobized by a water-insoluble amine compound, but did not contain a water-soluble amine compound, and therefore had inferior conductivity. Comparative Examples 5 to 9 contained a water-soluble amine compound, but did not contain a water-insoluble amine compound, and therefore the conductive complex did not become dispersible in an organic solvent.

Claims

1. The conductive composite material includes a π-conjugated conductive polymer and a polyanion, water, a water-insoluble amine compound, a water-soluble amine compound, and one or more organic solvents, The conductive polymer-containing liquid, wherein the polyanion is modified by reaction with at least the water-insoluble amine compound out of the water-insoluble amine compound and the water-soluble amine compound.

2. A method for producing a conductive polymer-containing liquid, comprising: adding an organic solvent, a water-insoluble amine compound, and a water-soluble amine compound to a conductive polymer dispersion liquid in which a conductive complex containing a π-conjugated conductive polymer and a polyanion is contained in an aqueous dispersion medium; and reacting at least the water-insoluble amine compound with the polyanion.

3. A method for producing a conductive laminate, comprising: applying the conductive polymer-containing liquid according to claim 1 or 2 to at least a part of a surface of a substrate.

4. 3. A conductive laminate comprising: a substrate; and a conductive layer formed on at least a partial surface of the substrate, the conductive layer being a cured layer of the conductive polymer-containing liquid according to claim 1.

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